Film adhesives containing maleimide compounds and methods for use thereof

ABSTRACT

In accordance with the present invention, there are provided film adhesive compositions comprising at least one macromonomer having at least one unit of ethylenic unsaturation, at least one thermoplastic elastomer co-curable with the macromonomer, and at least one cure initiator, and methods for use thereof. Invention compositions are useful as adhesives in the microelectronics industry. In particular, invention film adhesives may be used to produce microelectronic assemblies with very thin bond lines without compromising adhesive strength.

FIELD OF THE INVENTION

The present invention relates to film adhesive compositions, and moreparticularly to the use of film adhesive compositions in stacked diemicroelectronic packaging applications.

BACKGROUND OF THE INVENTION

In response to an increasing demand for semiconductor packages that aresmaller, yet more functional, the microelectronic packaging industry hasrecently begun producing packages containing at least two stackedsemiconductor dice. Indeed, it is often advantageous to stack multipledice into the same package in order to increase circuit density withoutincreasing the area occupied on a circuit board by the integratedcircuit package.

Several challenges exist with respect to producing reliable electroniccomponents containing stacked die packages. For example, stacked diepackages typically require very thin bond lines between die (e.g., <15microns). In addition, it is known that adhesive fillet and resin bleedassociated with many adhesive formulations contribute to unreliablecomponent performance. Thus, adhesives used in stacked die applicationsideally would provide (at a minimum bond line thickness) superioradhesive strength and conductivity (thermal and electrical) withoutproducing adhesive fillet or resin bleed. One possible approach toaddress this challenging problem lies in the use of film adhesives.

Accordingly, there is a need for film adhesives which provide superioradhesive strength and conductivity when dispensed to achieve very thinbond lines in a variety of microelectronic packages, such as, forexample, stacked die packages.

SUMMARY OF THE INVENTION

In accordance with the present invention, there are provided filmadhesive compositions comprising at least one macromonomer having atleast one unit of ethylenic unsaturation, at least one thermoplasticelastomer co-curable with the macromonomer, and at least one cureinitiator. Invention compositions are useful as adhesives in themicroelectronics industry. In particular, invention film adhesives maybe used to produce microelectronic assemblies with very thin bond lineswithout compromising adhesive strength.

In a further aspect of the present invention, there are provided methodsemploying invention film adhesive compositions for adhesively attachinga device to a substrate, and methods employing invention film adhesivecompositions for adhesively attaching at least two semiconductor dice toa substrate in a stacked arrangement.

In a still further aspect of the invention, there are providedassemblies comprising a first article adhered to a second article byinvention film adhesive compositions.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, there are provided adhesivecompositions comprising at least one macromonomer having at least oneunit of ethylenic unsaturation, at least one thermoplastic elastomerco-curable with the macromonomer, and at least one cure initiator.

As employed herein, “macromonomer” refers to a compound havingproperties suitable for use in invention film adhesive compositions. Forexample, macromonomers contemplated for use in the practice of thepresent invention typically are low melting point solids having lowvapor pressures. Alternatively, macromonomers contemplated for use inthe practice of the present invention may be liquids having a molecularweight of at least about 500 grams/mole.

As employed herein, “unit of ethylenic unsaturation” refers tounsaturation comprising localized (i.e., non-aromatic) carbon-carbondouble bonds, as shown below:

As employed herein, “co-curable” refers to the ability of athermoplastic elastomer to undergo copolymerization with a macromonomerto form a three-dimensional polymeric network.

Macromonomers contemplated for use in the practice of the presentinvention include, for example, maleimides, vinyl compounds, allylatedamides, and the like. In one embodiment, maleimide macromonomerscontemplated for use in the practice of the present invention includecompounds having the following structure:

wherein:

-   -   m=1-6,    -   R is independently selected from hydrogen or lower alkyl, and    -   X is a monovalent moiety or a multivalent linking moiety.

Monovalent moieties or multivalent linking moieties are typicallyselected from

-   -   (I) straight or branched chain alkyl, alkylene, oxyalkylene,        alkenyl, alkenylene, oxyalkenylene, ester, or polyester,        optionally containing substituents selected from hydroxy,        alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl,    -   (II) siloxanes having the structure:        —(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)— or        (CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)—        wherein    -    each R is independently defined as above, and each R′ is        independently selected from hydrogen, lower alkyl or aryl, m′        falls in the range of 1 up to 10, n′ falls in the range of 1 up        to 10, and q′ falls in the range of 1 up to 50,    -   (III) polyalkylene oxides having the structure:        —[(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)— or        [(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)—        wherein each R is independently as defined above, r falls in the        range of 1 up to 10, s falls in the range of 1 up to 10, and q′        is as defined above,    -   (IV) aromatic moieties having the structure:        wherein each R is independently as defined above, t falls in the        range of 2 up to 10, u is 1, 2 or 3, and Ar is as defined above,        or        wherein    -    Z is O or NR, wherein R is hydrogen or lower alkyl,    -   (V) urethanes having the structure        wherein:    -    each R₁ is independently hydrogen or lower alkyl,    -    each R₂ independently is an alkyl, aryl, or arylalkyl group        having 1 to 18 carbon atoms;    -    R₃ is an alkyl or alkyloxy chain having up to about 100 atoms        in the chain, which chain may contain aryl substituents;    -    X is O, S, N, or P; and    -    v is 0 to 50,    -   (VI) aromatic moieties having the structure:        wherein    -    each Ar is a monosubstituted, disubstituted or trisubstituted        aromatic or heteroaromatic ring having in the range of 3 up to        about 10 carbon atoms,    -    n is 1 up to about 50, and    -    Z is selected from:        -   straight or branched chain alkyl, alkylene, oxyalkylene,            alkenyl, alkenylene, oxyalkenylene, ester, or polyester,            optionally containing substituents selected from hydroxy,            alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl,        -   siloxanes having the structure:            —(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n)′—            wherein        -    each R is independently defined as above, and each R′ is            independently selected from hydrogen, lower alkyl or aryl,            m′ falls in the range of I up to 10, n′ falls in the range            of 1 up to 10, and q′ falls in the range of 1 up to 50,        -    polyalkylene oxides having the structure:            —[(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)—            wherein each R is independently as defined above, r falls in            the range of 1 up to 10, s falls in the range of 1 up to 10,            and q′ is as defined above,    -    aromatic moieties having the structure:        wherein each R is independently as defined above, t falls in the        range of 2 up to 10, u is 1, 2 or 3, and Ar is as defined above,    -   as well as mixtures of any two or more thereof.

As employed herein, “alkyl” refers to hydrocarbyl radicals having 1 upto about 20 carbon atoms, preferably 2-10 carbon atoms; and “substitutedalkyl” comprises alkyl groups further bearing one or more substituentsselected from hydroxy, alkoxy, mercapto, cycloalkyl, substitutedcycloalkyl, heterocyclic, substituted heterocyclic, aryl, substitutedaryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy,halogen, cyano, nitro, amino, amido, C(O)H, acyl, oxyacyl, carboxyl,carbamate, sulfonyl, sulfonamide, sulfuryl, and the like.

As employed herein, “cycloalkyl” refers to cyclic ring-containing groupscontaining in the range of 3 up to about 8 carbon atoms, and“substituted cycloalkyl” refers to cycloalkyl groups further bearing oneor more substituents as set forth above.

As employed herein, “alkenyl” refers to straight or branched chainhydrocarbyl groups having at least one carbon-carbon double bond, andhaving in the range of 2 up to about 12 carbon atoms, and “substitutedalkenyl” refers to alkenyl groups further bearing one or moresubstituents as set forth above.

As employed herein, “alkylene” refers to divalent hydrocarbyl radicalshaving 1 up to about 20 carbon atoms, preferably 2-10 carbon atoms; and“substituted alkylene” comprises alkylene groups further bearing one ormore substituents as set forth above.

As used herein, “oxyalkylene” refers to an alkylene moiety wherein oneor more of the methylene units of the alkylene moiety has been replacedwith an oxygen atom.

As employed herein, “aryl” refers to aromatic groups having in the rangeof 6 up to about 14 carbon atoms and “substituted aryl” refers to arylgroups further bearing one or more substituents as set forth above.

As employed herein, “alkenylene” refers to divalent, straight orbranched chain hydrocarbyl groups having at least one carbon-carbondouble bond, and having in the range of 2 up to about 12 carbon atoms,and “substituted alkenylene” refers to alkenylene groups further bearingone or more substituents as set forth above.

As employed herein, “oxyalkenylene” refers to an alkenylene moietywherein one or more of the methylene units of the alkenylene moiety hasbeen replaced with an oxygen atom.

Preferred maleimides contemplated for use in the practice of the presentinvention include, for example, maleimides having the followingstructures:

Vinyl macromonomers contemplated for use in the practice of the presentinvention include compounds having the following structure:

wherein:

-   -   q is 1, 2 or 3,    -   each R is independently selected from hydrogen or lower alkyl,    -   each Q is independently selected from —O—, —O—C(O)—, —C(O)— or        —C(O)—O—, and    -   Y is a monovalent moiety or a multivalent linking moiety.

The multivalent linking moiety Y is typically selected from:

-   -   (I) straight or branched chain alkyl, alkylene, oxyalkylene,        alkenyl, alkenylene, oxyalkenylene, ester, or polyester,        optionally containing substituents selected from hydroxy,        alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl,    -   (II) siloxanes having the structure:        —(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)— or        (CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)—        wherein    -    each R is independently defined as above, and each R′ is        independently selected from hydrogen, lower alkyl or aryl, m′        falls in the range of 1 up to 10, n′ falls in the range of 1 up        to 10, and q′ falls in the range of 1 up to 50,    -   (III) polyalkylene oxides having the structure:        —[(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)— or        [(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)—        wherein each R is independently as defined above, r falls in the        range of 1 up to 10, s falls in the range of 1 up to 10, and q′        is as defined above,    -   (IV) aromatic moieties having the structure:        wherein each R is independently as defined above, t falls in the        range of 2 up to 10, u is 1, 2 or 3, and Ar is as defined above,        or        wherein    -    Z is O or NR, wherein R is hydrogen or lower alkyl,    -   (V) urethanes having the structure        wherein:    -    each R₁ is independently hydrogen or lower alkyl,    -   each R₂ independently is an alkyl, aryl, or arylalkyl group        having 1 to 18 carbon atoms;    -    R₃ is an alkyl or alkyloxy chain having up to about 100 atoms        in the chain, which chain may contain aryl substituents;    -    X is O, S, N, or P; and    -    v is 0to50,    -   (VI) aromatic moieties having the structure:        wherein    -    each Ar is a monosubstituted, disubstituted or trisubstituted        aromatic or heteroaromatic ring having in the range of 3 up to        about 10 carbon atoms,    -    n is 1 up to about 50, and    -    Z is selected from:        -   straight or branched chain alkyl, alkylene, oxyalkylene,            alkenyl, alkenylene, oxyalkenylene, ester, or polyester,            optionally containing substituents selected from hydroxy,            alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl,        -   siloxanes having the structure:            —(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)—            wherein        -    each R is independently defined as above, and each R′ is            independently selected from hydrogen, lower alkyl or aryl,            m′ falls in the range of 1 up to 10, n′ falls in the range            of 1 up to 10, and q′ falls in the range of 1 up to 50,        -    polyalkylene oxides having the structure:            [(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)—            wherein each R is independently as defined above, r falls in            the range of 1 up to 10, s falls in the range of 1 up to 10,            and q′ is as defined above,    -    aromatic moieties having the structure:        wherein each R is independently as defined above, t falls in the        range of 2 up to 10, u is 1, 2 or 3, and Ar is as defined above,    -   as well as mixtures of any two or more thereof.

Allylated amide macromonomers contemplated for use in the practice ofthe present invention include compounds having the following structure:

wherein:

-   -   R′ is hydrogen, C₁ up to about C₁₈ alkyl or oxyalkyl, allyl,        aryl, or substituted aryl,    -   X is as defined above, and    -   m is 1-6.

Thermoplastic elastomers contemplated for use in the practice of thepresent invention are typically block copolymers. The block copolymershave at least one unit of the general formula (A-B), or (A-B-A), whereinA is a non-elastomeric polymer block and B is an elastomeric polymerblock. Block copolymers contemplated for use in the practice of thepresent invention preferably have low dielectric constants. In addition,thermoplastic elastomers contemplated for use in the practice of thepresent invention contain pendant and/or terminal units of ethylenicunsaturation, and therefore are able to cure with other components inthe adhesive composition, such as the unsaturated macromonomer.

In one aspect of the invention, the non-elastomeric polymer block (A) isthe polymerization product of one or more optionally substitutedaromatic hydrocarbons containing at least one unit of ethylenicunsaturation. Aromatic hydrocarbons contemplated for use in the practiceof the present invention include, for example, optionally substitutedstyrene, optionally substituted stilbene, and the like. Substituentscontemplated for optional use in the practice of the present inventioninclude for example, alkyl, alkenyl, alkynyl, hydroxy, alkoxy, alkenoxy,and the like. In a preferred embodiment, the aromatic hydrocarbon isoptionally substituted styrene.

The elastomeric polymer block (B) is typically the polymerization orcopolymerization product of optionally substituted olefin monomersand/or optionally substituted conjugated diene monomers. Olefin monomerscontemplated for use in the practice of the present invention typicallycontain from 2 up to about 20 carbon atoms. Preferably, the olefinmonomers contain from 2 up to about 12 carbon atoms. In a particularlypreferred embodiment, the olefin monomers include, for example,ethylene, propylene, butylene, isobutylene, acrylonitrile,(meth)acrylate, and the like. Most preferably, the olefin monomer isacrylonitrile.

Conjugated diene monomers contemplated for use in the practice of thepresent invention typically contain from 4 up to about 20 carbon atoms.Preferably, the conjugated diene monomers contain from 4 up to about 12carbon atoms. In a particularly preferred embodiment, the conjugateddiene monomers include, for example, butadiene, isoprene,dimethylbutadiene, and the like. Most preferably, the conjugated dienemonomer is butadiene.

The structure of the elastomeric segments can be optionally modified toincrease adhesive strength of invention compositions. For example, theelastomeric segments of the block copolymers (e.g., the polybutadienesegments) may be modified via a thermally induced ene-reaction withmaleic anhydride (for a review of the ene-reaction, see, for example,Oppolzer, W., Snieckus, V., Angew. Chem. Int. Ed. Engl., 1978, 17, 476).Such modification has a particularly positive impact on hot die-shearvalues.

Thermoplastic elastomers contemplated for use in the practice of thepresent invention include, for example,polystyrene-polybutadiene-polystyrene block copolymers,polystyrene-polyisoprene-polystyrene block copolymers,polystyrene-polydimethylbutadiene-polystyrene block copolymers,polybutadiene-polyacrylonitrile block copolymers, and the like.Preferably, the block copolymer is apolystyrene-polybutadiene-polystyrene block copolymer or apolybutadiene-polyacrylonitrile block copolymer.

Adhesive compositions of the invention also contain in the range of 0.2up to 2 weight % of at least one free radical initiator, wherein weight% (wt %) is based on the total weight of the composition. As employedherein, the term “free radical initiator” refers to any chemical specieswhich, upon exposure to sufficient energy (e.g., light, heat, or thelike), decomposes into at least two species which are uncharged, butwhich each possesses at least one unpaired electron. Preferred freeradical initiators contemplated for use in the practice of the presentinvention are compounds which decompose (i.e., have a half life in therange of about 10 hours) at temperatures in the range of about 70 up to180° C.

Free-radical cure initiators contemplated for use in the practice of thepresent invention include for example, peroxides (e.g., peroxy esters,peroxy carbonates, hydroperoxides, alkylperoxides, arylperoxides, andthe like), azo compounds, and the like. Presently preferred peroxidescontemplated for use in the practice of the present invention includedicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butylperbenzoate, di-tert-butyl peroxide,2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, bis(tert-butylperoxyisopropyl)benzene, tert-butyl hydroperoxide, and the like.Presently preferred azo compounds contemplated for use in the practiceof the present invention include 2,2′-azobis(2-methylpropanenitrile),2,2′-azobis(2-methylbutanenitrile),1,1′-azobis(cyclohexanecarbonitrile), and the like.

Adhesive compositions contemplated for use in the practice of thepresent invention typically contain in the range of about 10 wt % up toabout 95 wt % thermoplastic elastomer, in the range of about 5 wt % upto about 90 wt % macromonomer having at least one unit of ethylenicunsaturation, and in the range of about 0.5 wt % up to about 2.0 wt % acure initiator, wherein weight % is based on the total weight of thecomposition. Preferably, the macromonomer having at least one unit ofethylenic unsaturation is present in the range of about 10 wt % up toabout 80 wt %.

Adhesive compositions according to the invention optionally furthercontain in the range of about 0.1 up to about 10 wt % of at least onecoupling agent, based on the total weight of the composition.Preferably, the coupling agent is present in the range of about 0.2 wt %up to about 5 wt %. Coupling agents contemplated for use in the practiceof the present invention include siloxanes, silicate esters, metalacrylate salts, titanates, and the like.

Adhesive compositions according to the invention may optionally containa filler. Fillers contemplated for optional use in the practice of thepresent invention may optionally be conductive (electrically and/orthermally). Electrically conductive fillers contemplated for use in thepractice of the present invention include, for example, silver, nickel,gold, cobalt, copper, aluminum, graphite, silver-coated graphite,nickel-coated graphite, alloys of such metals, and the like, as well asmixtures thereof. Both powder and flake forms of filler may be used inthe adhesive compositions of the present invention. Preferably, theflake has a thickness of less than about 2 microns, with planardimensions of about 20 to about 25 microns. Flake employed hereinpreferably has a surface area of about 0.15 to 5.0 m²/g and a tapdensity of about 0.4 up to about 5.5 g/cc. It is presently preferredthat powder employed in the practice of the invention has a diameter ofabout 0.5 to 15 microns. If present, the filler typically comprises inthe range of about 1 wt % up to about 95 wt % of the adhesiveformulation, wherein weight % is based on the total weight of thecomposition.

Thermally conductive fillers contemplated for optional use in thepractice of the present invention include, for example, aluminumnitride, boron nitride, silicon carbide, diamond, graphite, berylliumoxide, magnesia, silica, alumina, and the like. Preferably, the particlesize of these fillers will be in the range of about 5 up to about 30microns. Most preferably, the particle size of these fillers will beabout 20 microns.

Electrically and/or thermally conductive fillers are optionally (andpreferably) rendered substantially free of catalytically active metalions by treatment with chelating agents, reducing agents, nonioniclubricating agents, or mixtures of such agents. Such treatment isdescribed in U.S. Pat. No. 5,447,988, which is incorporated by referenceherein in its entirety.

Optionally, a filler may be used that is neither an electrical northermal conductor. Such fillers may be desirable to impart some otherproperty to the adhesive formulation such as, for example, reducedthermal expansion of the cured adhesive, reduced dielectric constant,improved toughness, increased hydrophobicity, and the like. Examples ofsuch fillers include perfluorinated hydrocarbon polymers (i.e.,TEFLON™), thermoplastic polymers, thermoplastic elastomers, mica, fusedsilica, glass powder, and the like.

In a preferred embodiment, adhesive compositions contemplated for use inthe practice of the present invention contain in the range of about 5 wt% up to about 90 wt % thermoplastic elastomer, in the range of about 5wt % up to about 90 wt % macromonomer containing at least one unit ofethylenic unsaturation, in the range of about 0.5 wt % up to about 2.0wt % cure initiator, in the range of about 0.5 wt % up to about 5 wt %coupling agent, and in the range of about 1 wt % up to about 95 wt %filler, wherein weight % is based on the total weight of thecomposition.

In a further aspect of the invention, there are provided methods foradhesively attaching a device to a substrate comprising subjecting asufficient quantity of an invention adhesive composition positionedbetween a substrate and a device to conditions suitable to cure theadhesive formulation. Devices contemplated for use in the practice ofthe present invention include any surface mount component such as, forexample, semiconductor die, resistors, capacitors, and the like.Preferably, devices contemplated for use in the practice of inventionmethods are semiconductor dies. Substrates contemplated for use includemetal substrates (e.g., lead frames), organic substrates (e.g.,laminates, ball grid arrays, polyamide films), and the like.

Conditions suitable to cure invention film adhesive compositionscomprise subjecting invention film adhesive compositions to atemperature of at least about 150° C. but less than about 300° C. forabout 0.5 up to about 2 minutes. This rapid, short duration heating canbe accomplished in a variety of ways, e.g., with an in-line heated rail,a belt furnace, or the like.

Alternatively, conditions suitable to cure invention film adhesivecompositions comprise subjecting invention film adhesive compositions toa temperature in the range of about 120° C. up to about 200° C. for aperiod of about 15 minutes up to about 60 minutes. These conditions canbe readily produced in a variety of ways, such, for example, by placinginvention film adhesive compositions in a curing oven.

In a still further aspect of the invention, there are provided methodsfor adhesively attaching at least two semiconductor dice to a substratein a stacked arrangement comprising curing a sufficient quantity of aninvention adhesive composition positioned between the substrate and eachof the die.

In yet another aspect of the present invention, there are providedassemblies comprising a first article permanently adhered to a secondarticle by a sufficient quantity of an invention adhesive composition.

The invention will now be described in greater detail by reference tothe following non-limiting example.

EXAMPLE

An adhesive composition according to the present invention was preparedas follows. Invention Formulation 1 was prepared using thestyrene-butadiene block copolymer KRATON™ D-1102 as the thermoplasticelastomeric component. Octadecylmaleimide and X-BMI (X-BMI is the1,20-bismaleimido derivative of 10,11-dioctyl-eicosane) were employed asmacromonomers. The maleimides used in the following inventionformulations were prepared according to the procedure set forth in U.S.Pat. No. 5,973,166, the entire contents of which are incorporated byreference herein. Invention Formulation 1 1. Octadecylmaleimide  1.0 g2. KRATON ™ D-1102  2.5 g 3. X-BMI  1.5 g 4. Ricon 130¹  0.2 g 5. Silanecoupling agent²  0.2 g 6. Dicumyl peroxide 0.05 g 7. Xylene  5.0 g 8.TEFLON ™ filler  6.9 g¹Polybutadiene 20% grafted with maleic anhydride (Sartomer)²Proprietary silane-containing coupling agent.

Preparation of Formulation 1 began by dissolving octadecylmaleimide inxylene. KRATON was added to this solution and allowed to dissolvecompletely before the remaining components were added.

A film of Invention Formulation 1 was cast onto a glass substrate anddried overnight. A silicon die was then placed onto the film, and thefilm-coated substrate was heated to 80° C. for 1 to 3 seconds. Thisassembly was finally cured at 185° C. for 30 minutes.

The film adhesive compositions were tested for room temperature dieshear and hot die shear on a calibrated Dage 2400 die shear tester. Theresults for Invention Formulation 1 are shown below in Table 1, comparedto QMI536, a non-film adhesive formulation (prepared according to U.S.Pat. No. 5,717,034) comprising the same maleimides as employed for thepreparation of Invention Formulation 1. Also included in Table 1 are dieshear values after the cured compositions were subjected to 85° C./85%humidity for 24 hrs. TABLE 1 Room Temperature Hot Die Shear Die Shear(lbs) (245° C.) (lbs) QMI536, initial 59.1 24.4 Invention Formulation 1,initial 88.9 25.9 QMI536, 24 hrs. 85/85 52.6 23.9 Invention Formulation1, 24 hrs. 79.6 24.6 85/85

The results shown above demonstrate that Invention Formulation 1 hassuperior adhesive strength compared to an analogous non-film formingcomposition.

While the invention has been described in detail with reference tocertain preferred embodiments thereof, it will be understood thatmodifications and variations are within the spirit and scope of thatwhich is described and claimed.

1-15. (canceled)
 16. A thermally curable film adhesive compositioncomprising a curable component comprising at least one macromonomerhaving at least one unit of ethylenic unsaturation, wherein saidmacromonomer is a maleimide, in the range of about 20-90 wt % of atleast one thermoplastic elastomer co-curable with said at least onemacromonomer, and at least one free radical cure initiator, wherein wt %is based on total weight of the composition; and wherein said freeradical cure initiator is present in the range of about 0.5 wt % up to2.0 wt %; and wherein said macromonomer is present in the range of about10 wt % up to about 80 wt %, wherein wt % is based on total weight ofthe composition.
 17. An adhesive composition according to claim 16,wherein said cure initiator is a free-radical cure initiator. 18-21.(canceled)
 22. An adhesive composition according to claim 16, furthercomprising a filler.
 23. An adhesive composition according to claim 22,wherein said filler is conductive.
 24. An adhesive composition accordingto claim 23, wherein said filler is electrically conductive.
 25. Anadhesive composition according to claim 23, wherein said filler isthermally conductive.
 26. An adhesive composition according to claim 22,wherein said filler is non-conductive.
 27. An adhesive compositionaccording to claim 26, wherein said filler is a perfluorinatedhydrocarbon polymer.
 28. An adhesive composition according to claim 22,wherein said filler is present in the range of about 1 wt % up to about95 wt %, wherein wt % is based on total weight of the composition. 29.(canceled)
 30. An adhesive composition comprising at least onethermoplastic elastomer, at least one macromonomer having at least oneunit of ethylenic unsaturation, and at least one cure initiator, whereinsaid macromonomer is selected from the group consisting of maleimides,allylated amides, and vinyl compounds.
 31. An adhesive compositionaccording to claim 30, wherein said composition is capable of curing ata temperature in the range of about 150° C. up to about 200° C. in aperiod of time of about 0.25 minutes up to about 2 minutes. 32-34.(canceled)
 35. An adhesive composition according to claim 30, whereinsaid macromonomer is a vinyl compound.
 36. An adhesive compositionaccording to claim 35, wherein said vinyl compound has the followingstructure:

wherein: q is 1, 2 or 3, each R is independently selected from hydrogenor lower alkyl, each Q is independently selected from —O—, —O—C(O)—,—C(O)— or —C(O)—O—, and Y is a monovalent moiety or a multivalentlinking moiety.
 37. An adhesive composition according to claim 36,wherein Y is selected from: (I) straight or branched chain alkyl,alkylene, oxyalkylene, alkenyl, alkenylene, oxyalkenylene, ester, orpolyester, optionally containing substituents selected from hydroxy,alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl, (II) siloxaneshaving the structure:—(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)— or(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si (R′)₂—(CR₂)_(n′)— wherein  each R isindependently defined as above, and each R′ is independently selectedfrom hydrogen, lower alkyl or aryl, m′ falls in the range of 1 up to 10,n′ falls in the range of 1 up to 10, and q′ falls in the range of 1 upto 50, (III) polyalkylene oxides having the structure:—[(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)— or(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)— wherein each R is independently as definedabove, r falls in the range of 1 up to 10, s falls in the range of 1 upto 10, and q′ is as defined above, (IV) aromatic moieties having thestructure:

wherein each R is independently as defined above, t falls in the rangeof 2 up to 10, u is 1, 2 or 3, and Ar is as defined above, or

wherein Z is O or NR, wherein R is hydrogen or lower alkyl, (V)urethanes having the structure

wherein:  each R₁ is independently hydrogen or lower alkyl,  each R₂independently is an alkyl, aryl, or arylalkyl group having 1 to 18carbon atoms;  R₃ is an alkyl or alkyloxy chain having up to about 100atoms in the chain, which chain may contain aryl substituents;  X is O,S, N, or P; and  v is 0 to 50, (VI) aromatic moieties having thestructure:

wherein  each Ar is a monosubstituted, disubstituted or trisubstitutedaromatic or heteroaromatic ring having in the range of 3 up to about 10carbon atoms,  n is 1 up to about 50, and  Z is selected from: straightor branched chain alkyl, alkylene, oxyalkylene, alkenyl, alkenylene,oxyalkenylene, ester, or polyester, optionally containing substituentsselected from hydroxy, alkoxy, carboxy, nitrile, cycloalkyl orcycloalkenyl, siloxanes having the structure:—(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)— wherein  each R isindependently defined as above, and each R′ is independently selectedfrom hydrogen, lower alkyl or aryl, m′ falls in the range of 1 up to 10,n′ falls in the range of 1 up to 10, and q′ falls in the range of 1 upto 50,  polyalkylene oxides having the structure:—[(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)— wherein each R is independently asdefined above, r falls in the range of 1 up to 10, s falls in the rangeof 1 up to 10, and q′ is as defined above, aromatic moieties having thestructure:

wherein each R is independently as defined above, t falls in the rangeof 2 up to 10, u is 1, 2 or 3, and Ar is as defined above, as well asmixtures of any two or more thereof.
 38. An adhesive compositionaccording to claim 30, wherein said macromonomer is an allylated amide.39. An adhesive composition according to claim 38, wherein saidallylated amide has the following structure:

wherein: R′ is hydrogen, C₁ up to about C₁₈ alkyl or oxyalkyl, allyl,aryl, or substituted aryl, m is 1-6, and X is selected from (I) straightor branched chain alkyl, alkylene, oxyalkylene, alkenyl, alkenylene,oxyalkenylene, ester, or polyester, optionally containing substituentsselected from hydroxy, alkoxy, carboxy, nitrile, cycloalkyl orcycloalkenyl, (II) siloxanes having the structure:—(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)— or(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)— wherein  each R isindependently defined as above, and each R′ is independently selectedfrom hydrogen, lower alkyl or aryl, m′ falls in the range of 1 up to 10,n′ falls in the range of 1 up to 10, and q′ falls in the range of 1 upto 50, (III) polyalkylene oxides having the structure:—[(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)— or[(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)— wherein each R is independently asdefined above, r falls in the range of 1 up to 10, s falls in the rangeof 1 up to 10, and q′ is as defined above, (IV) aromatic moieties havingthe structure:

wherein each R is independently as defined above, t falls in the rangeof 2 up to 10, u is 1, 2 or 3 and Ar is as defined above, or

wherein  Z is O or NR, wherein R is hydrogen or lower alkyl, (V)urethanes having the structure

wherein:  each R₁ is independently hydrogen or lower alkyl,  each R₂independently is an alkyl, aryl, or arylalkyl group having 1 to 18carbon atoms;  R₃ is an alkyl or alkyloxy chain having up to about 100atoms in the chain, which chain may contain aryl substituents;  X is O,S, N, or P; and  v is 0 to 50, (VI) aromatic moieties having thestructure:

wherein  each Ar is a monosubstituted, disubstituted or trisubstitutedaromatic or heteroaromatic ring having in the range of 3 up to about 10carbon atoms,  n is 1 up to about 50, and  Z is selected from: straightor branched chain alkyl, alkylene, oxyalkylene, alkenyl, alkenylene,oxyalkenylene, ester, or polyester, optionally containing substituentsselected from hydroxy, alkoxy, carboxy, nitrile, cycloalkyl orcycloalkenyl, siloxanes having the structure:(CR₂)_(m′)—[Si(R′)₂—O]_(q′)—Si(R′)₂—(CR₂)_(n′)— wherein  each R isindependently defined as above, and each R′ is independently selectedfrom hydrogen, lower alkyl or aryl, m′ falls in the range of 1 up to 10,n′ falls in the range of 1 up to 10, and q′ falls in the range of 1 upto 50,  polyalkylene oxides having the structure:—[(CR₂)_(r)—O—]_(q′)—(CR₂)_(s)— wherein each R is independently asdefined above, r falls in the range of 1 up to 10, s falls in the rangeof 1 up to 10, and q′ is as defined above, aromatic moieties having thestructure:

wherein each R is independently as defined above, t falls in the rangeof 2 up to 10, u is 1, 2 or 3, and Ar is as defined above, as well asmixtures of any two or more thereof. 40-45. (canceled)
 46. An adhesivecomposition comprising at least one macromonomer having at least oneunit of ethylenic unsaturation, at least one thermoplastic elastomerco-curable with said at least one macromonomer, and at least one cureinitiator, which when dispensed between a device and a substrate andcured for 2 minutes at 200° C., provides a room temperature die shear ofabout 90 lbs.
 47. An adhesive composition according to claim 46, whereinsaid macromonomer is a maleimide.